Uni Reading List
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Molecular Thermodynamics cover

Chemistry

Chemistry

Molecular Thermodynamics

Donald A. McQuarrie and John D. Simon

A molecular approach to thermodynamics that develops statistical mechanics, equilibrium, phase behavior, and the connection between microscopic models and macroscopic chemistry.

Prerequisites: Multivariable calculus with partial derivatives, general chemistry, and some exposure to quantised energy levels.

Difficulty Level
Intermediate
Academic Level
Undergraduate
thermodynamicsstatistical mechanicsmolecular chemistryequilibriumphysical chemistry

01 / Reading Guide

Reading Guide

Citation

McQuarrie, D. A., & Simon, J. D. (1999). Molecular Thermodynamics. University Science Books.

Chapter Summary

The book has fourteen chapters and about 650 pages, interleaved with five short "MathChapters" that review mathematical tools. It grew out of the authors' larger textbook Physical Chemistry: A Molecular Approach and keeps the thermodynamics part of that course, with three chapters written for this book: on the energy levels of atoms and molecules, on electrochemical cells, and on nonequilibrium thermodynamics. The sequence is molecular first: energy levels and partition functions are introduced before the laws of thermodynamics, which are then developed alongside their statistical interpretation.

Chapters 1–4: The Energy Levels of Atoms and Molecules; Properties of Gases; The Boltzmann Factor and Partition Functions; Partition Functions and Ideal Gases

The opening chapters set up the molecular description. Chapter 1 presents the energy levels of atoms and molecules, the input that statistical thermodynamics needs, and Chapter 2 treats the properties of gases. Chapters 3 and 4 introduce the Boltzmann factor, partition functions and their application to ideal gases, so that macroscopic properties can be computed from molecular energy levels from the start.

Chapters 5–7: The First Law of Thermodynamics; Entropy and the Second Law of Thermodynamics; Entropy and the Third Law of Thermodynamics

The three laws are developed in turn. The first-law chapter is followed by two chapters on entropy, one on the second law and one on the third.

Chapter 8: Helmholtz and Gibbs Energies

The free energies that decide the direction of change at constant volume and constant pressure, which the later chapters on equilibrium rely on.

Chapters 9–11: Phase Equilibrium; Solutions I: Liquid-Liquid Solutions; Solutions II: Solid-Liquid Solutions

Phase behaviour of pure substances, followed by two chapters on solutions, one on liquid–liquid mixtures and one on solid–liquid mixtures.

Chapter 12: Chemical Equilibrium

Equilibrium in chemical reactions, building on the free energies and the statistical treatment of earlier chapters.

Chapters 13–14: Thermodynamics of Electrochemical Cells; Nonequilibrium Thermodynamics

Two of the three chapters that the publisher flags as new to this book. Chapter 13 applies thermodynamics to electrochemical cells, and Chapter 14 turns to systems that are not at equilibrium.

MathChapters

Five short chapters, each with its own set of problems, review the mathematical tools the text depends on: numerical methods; probability and statistics; series and limits; partial differentiation; and the binomial distribution with Stirling's approximation.

Key Concepts

Chapters 1–4

  • Energy levels: the allowed energies of atoms and molecules, which are the basis of the statistical description.
  • Boltzmann factor: the weight that gives the probability of finding a system in a state of a given energy.
  • Partition function: a sum over states from which thermodynamic quantities follow.

Chapters 5–8

  • First, second and third laws: energy conservation, entropy increase and the limiting value of entropy at low temperature.
  • Helmholtz and Gibbs energies: functions that determine the direction of spontaneous change under constraints.

Chapters 9–14

  • Phase equilibrium: the conditions under which phases coexist.
  • Solution thermodynamics: liquid–liquid and solid–liquid mixtures.
  • Chemical equilibrium and electrochemical cells: equilibrium conditions for reactions, and their expression in cell potentials.
  • Nonequilibrium thermodynamics: the description of systems away from equilibrium.

Critical Analysis

Strengths

  • Molecular viewpoint from the start. Partition functions arrive in Chapters 3–4, before entropy and free energy, so the later thermodynamic results can be tied back to molecular energy levels. The publisher describes the text as a molecular approach to thermodynamics.
  • Self-contained mathematics. The five MathChapters, each with problems, let a reader refresh the specific tools used (partial differentiation, series, probability, Stirling's approximation) without leaving the book.
  • Practice material. The publisher states that worked examples and chapter-ending problems with solutions are included throughout, and a separate problems-and-solutions volume exists for the text.
  • Reception. A reviewer quoted in the bookseller's listing, from the Journal of Statistical Physics, called the book a downsized, more digestible version of the authors' larger physical chemistry text.

Limitations

  • Only the thermodynamics portion. The book leaves out the quantum chemistry, spectroscopy and kinetics of a full physical chemistry course; readers who need those must use a general physical chemistry text.
  • Mathematically demanding. Five MathChapters on partial differentiation, series, probability and related tools show how much calculus and statistics the text expects; readers without that background will need to work through them.
  • Dated. The book is a 1999 publication, so later developments in teaching and in the subject are not reflected.

Where It Fits in the Course

In the physical chemistry course this is a focused text for thermodynamics with a statistical-mechanical backbone. Atkins's Physical Chemistry is the comprehensive undergraduate text covering thermodynamics, quantum theory, spectroscopy, statistical thermodynamics and kinetics in one volume; McQuarrie and Simon's book covers a narrower area but introduces the statistical treatment earlier. Chang's Physical Chemistry for the Chemical and Biological Sciences is an accessible treatment for students across chemistry and biology and Monk's Physical Chemistry: Understanding our Chemical World is written for first-year students, so both come before it. Atkins's Physical Chemistry: A Very Short Introduction is a brief, almost equation-free overview for orientation.

A natural pairing is a general text for the course as a whole and Molecular Thermodynamics as a second source for the thermodynamics-plus-statistical-mechanics sequence, or as the main text in a course devoted to that topic.

How to Use This Book

The book is for chemistry students who have completed general chemistry and calculus with partial derivatives and who have met the idea of quantised energy levels. It suits a one-semester course or self-study in chemical thermodynamics with molecular interpretation.

A practical plan:

  • Read Chapters 1–4 first, even if thermodynamics has been seen before, since the later chapters interpret thermodynamic quantities through energy levels and partition functions.
  • Use the MathChapters when needed, at the point where partial differentiation, probability or Stirling's approximation first appears.
  • Core thermodynamics: Chapters 5–8 and then 9–12 for phase and chemical equilibrium.
  • Optional extensions: Chapter 13 for electrochemistry and Chapter 14 for nonequilibrium systems.
  • Work the problems in each chapter and in the MathChapters; the separate problems-and-solutions volume can be used to check results.